CHM3120C Analytical Chemistry Lab

Lab 2. The Gravimetric Determination of Chloride in a Soluble Sample

**Required Reagents and Supplies (for 4 groups: group of 3): 9 sintered-glasses, 6 M
NH3, conc. HNO3, minimum 10 mL of 6 M HNO3, minimum 3 g of dried soluble chlorides
(unknowns), minimum 300 mL of 0.2 M AgNO3, the aluminum foils, and the waste
container.
I. Introduction: Gravimetric analysis is a method based on the isolation of the desired
constituent in pure form or in some combined form from a sample, and weighing the
isolated constituent. The desired constituent is usually isolated or separated by
precipitation. From the weights of sample and precipitate, the percentage of constituent can
be calculated.
The sample to be analyzed for chloride content is a solid crystalline powder containing a
mixture of chloride salts (e.g., KCl, NaCl) as well as some inert (unreactive and noninterfering) material. The objective is to determine the chloride composition (percent) of
the sample by first dissolving an accurately weighed portion of the sample, and then
separating the chloride from other ions by reacting it selectively with silver ion to form
insoluble silver chloride. The silver chloride precipitate is collected quantitatively and
subsequently purified and weighed. The mass of chloride contained in the silver chloride
precipitate should be identical to that originally contained in the weighed sample mixture;
thus, the weight percent chloride in the original sample can be calculated (to four
significant figures).
Silver ions undergo the following reaction with chloride:
Ag+

Cl-

AgCl (white solid)

Silver chloride is a relatively insoluble compound with a solubility product (Ksp = [Ag+]
[Cl-]) of 1.8 x 10-10. An excess of silver ions is added so that the chloride concentration at
equilibrium will be negligible. If enough silver nitrate solution is not used, the precipitation
will be incomplete, resulting in a substantial error and a low value for the % Cl in the
sample.

The precipitate is collected in a weighed filtering crucible and is washed. After the
precipitate has been dried to a constant mass at 110 C, its mass is determined. The solution
containing the sample is kept slightly acidic during the precipitation to eliminate possible
interference from anions of weak acids (such as CO32-) that form sparingly soluble silver
salts in a neutral environment. A moderate excess of silver ion is needed to diminish the
solubility of silver chloride, but large excess is avoided to minimize coprecipitation of
silver nitrate.
Silver chloride forms first as a colloid and is subsequently coagulated with heat. Nitric acid
and the small excess of silver nitrate promote coagulation by providing a moderately high
electrolyte concentration. Nitric acid in the wash solution maintains the electrolyte
concentration and eliminates the possibility of peptization during the washing step; the acid
subsequently decomposes to give volatile products when the precipitate is dried.
In common with other silver halides, finely divided silver chloride undergoes
photodecomposition:
2AgCl(s)

2Ag(s)

Cl2(g)

The elemental silver produced in this reaction is responsible for the violet color that
develops in the precipitate. In principle, this reaction leads to low results for chloride
ion. In practice, however, its effect is negligible provided that direct and prolonged
exposure of the precipitate to sunlight is avoided.
If photodecomposition of silver chloride occurs before filtration, the additional reaction
tends to cause high results.
3Cl2(aq)

3H2O

5Ag+

5AgCl(s)

ClO3-

6H+

In the usual procedure, some photodecomposition of silver chloride is inevitable. It is

worthwhile to minimize exposure of the solid to intense sources of light as much as
possible.
Because silver nitrate is expensive, any unused reagent should be collected in a storage
container; similarly, precipitated silver chloride should be retained after the analysis is
complete.

Warning! You must wear gloves. Avoid contact of AgNO3 with skin. Decomposition of
AgNO3 on skin gives black spots.
II. Procedure: Sintered-glasses are ready to use. You may start from Step g.
Part 1
a. Clean three medium-porosity sintered-glasses by allowing about 5 mL of concentrated
HNO3 to stand in each for about 5 min.
b. Use a vacuum (see Figure 2-16 in the textbook) to draw the acid through the crucible.
Rinse each crucible with three portions of tap water, and then discontinue the vacuum.
c. Add about 5 mL of 6 M NH 3 and wait for about 5 min before drawing it through the
filter.
d. Rinse each crucible with six to eight portions of distilled or deionized water. Provide
each crucible with an identifying mark.
e. Dry the crucibles to constant mass by heating at 110C while the other steps in the
analysis are being carried out. The first drying should be for at least 1 hr; subsequent
heating periods can be somewhat shorter (30 to 40 min). This process of heating and drying
should be repeated until the mass becomes constant to within 0.2 to 0.3 mg.
f. Transfer the unknown to a weighing bottle and dry it at 110C (see Lab 1. manual) for 1
to 2 hr.
g. Bring a clean and dry weighing bottle to obtain the unknown from TA, then keep the
weighing bottle in a desiccator for 5 minutes for cooling.
h. Using the weigh-by-difference technique, accurately weigh out (to the nearest 0.0001 g)
three unknown samples, of 0.25 to 0.30 g each, into 400-mL beakers. You may use a
weighing paper to weigh the unknown, but make sure to transfer the unknown
quantitatively into the 400 mL beaker.
i. Dissolve each sample in about 100 mL of distilled water, and add 2 to 3 mL of 6 M
HNO3.
j. Slowly, and with good stirring, add 0.2 M AgNO3 to each of the cold sample solutions
until AgCl is observed to coagulate*.

*Tip: Remember, you may need ~ 30 mL of 0.2 M AgNO 3 in total for each trial, so first
add whole ~ 15 mL of 0.2 M AgNO 3 at once to save your time before you proceed to
Step k.
k. Heat almost to boiling, and digest (heat unstirred solids in mother liquor) the solids for
about 10 min. Add a few drops of AgNO3 to confirm that precipitation is complete. If more
precipitate forms, add additional 3-5 mL of AgNO 3, digest, and again test for completeness
of precipitation. Pour any unused AgNO3 into a waste container (not into the original
reagent bottle).
l. Cover each beaker with aluminum foil, and store in a dark place for at least 2 hr
(preferably until the next laboratory period).
Part 2
1. Vacuum Filtration and Drying
a. Obtain three sintered-glasses from the oven, cool to room temperature, and label them.
b. Set up the vacuum filtration, and decant the supernatant liquids through weighed
sintered-glasses under the vacuum.
c. Wash the precipitates several times (while they are still in the beaker) with a solution
consisting of 1 to 3 mL of 6 M HNO3 per 500 mL of distilled water; decant these washings
through the filters.
d. Quantitatively transfer the AgCl from the beakers to the individual sintered-glasses with
fine streams of wash solution (diluted HNO3 solution); use rubber policemen to dislodge
any particles that adhere to the walls of the beakers. Continue washing until the filtrates are
essentially free of Ag+ ion.
e. Dry the precipitate at 110C for at least 1 hr (preferably until the next laboratory period).
Follow the proper procedure for drying samples (See Lab 1 manual.). Store the sinteredglasses in a desiccator while they cool to room temperature.
g. Determine the mass of the product in the sintered-glass. Calculate the percentage of Clin the sample.
II. Calculations

Gravimetric Factor (G.F.) =

molar mass of Cl (=35.453 g/mol)

molar mass of AgCl (=143.321 g/mol)

So, the mass of chlorine in each sample = mass of the precipitate (AgCl) x G.F.
Finally,
% Cl- in each sample =

mass of chlorine in each sample

x 100%
mass of the unknown

III. Waste Proposal: When the analysis is complete, remove the precipitates by gently
tapping the crucibles over a piece of glazed paper. Transfer the collected AgCl(s) to a
container for silver wastes.